materials

Article
Injection Molding of 3-3 Hydroxyapatite Composites
Jonas Biggemann 1 , Patrizia Hoffmann 1 , Ivaylo Hristov 1 , Swantje Simon 1 , Philipp Müller 1 and
Tobias Fey 1,2, *
1 Department of Materials Science (Glass and Ceramics), University of Erlangen-Nuernberg, Martensstr. 5,
D-91058 Erlangen, Germany; jonas.biggemann@fau.de (J.B.); patrizia.hoffmann@fau.de (P.H.);
Ivaylo.Hristov@fau.de (I.H.); Swantje.Simon@fau.de (S.S.); philipp.georg.mueller@fau.de (P.M.)
2 Frontier Research Institute for Materials Science, Nagoya Institute of Technology, Gokiso-cho, Showa-ku,
Nagoya 466-8555, Japan
* Correspondence: tobias.fey@fau.de; Tel.: +49-9131-8527546




Received: 4 April 2020; Accepted: 15 April 2020; Published: 17 April 2020


Abstract: The manufacturing of ideal implants requires fabrication processes enabling an adjustment
of the shape, porosity and pore sizes to the patient-specific defect. To meet these criteria novel
porous hydroxyapatite (HAp) implants were manufactured by combining ceramic injection molding
(CIM) with sacrificial templating. Varied amounts (Φ = 0–40 Vol%) of spherical pore formers with a
size of 20 µm were added to a HAp-feedstock to generate well-defined porosities of 11.2–45.2 Vol%
after thermal debinding and sintering. At pore former contents Φ ≥ 30 Vol% interconnected pore
networks were formed. The investigated Young’s modulus and flexural strength decreased with
increasing pore former content from 97.3 to 29.1 GPa and 69.0 to 13.0 MPa, agreeing well with a fitted
power-law approach. Additionally, interpenetrating HAp/polymer composites were manufactured by
infiltrating and afterwards curing of an urethane dimethacrylate-based (UDMA) monomer solution
into the porous HAp ceramic preforms. The obtained stiffness (32–46 GPa) and Vickers hardness
(1.2–2.1 GPa) of the HAp/UDMA composites were comparable to natural dentin, enamel and other
polymer infiltrated ceramic network (PICN) materials. The combination of CIM and sacrificial
templating facilitates a near-net shape manufacturing of complex shaped bone and dental implants,
whose properties can be directly tailored by the amount, shape and size of the pore formers.

Keywords: ceramic injection molding; sacrificial templating; porous hydroxyapatite; interpenetrating

composites; bone grafts; dental implants

1. Introduction
The restoration of large bone defects represents one of the key issues in current orthopedic and
trauma surgery [1,2]. Especially critical bone defects, arising from diseases (such as osteoporosis),
tumor surgeries or fractures in all kinds of sizes and shapes, cannot naturally be self-repaired [3–5].
Unlimited and patient individualized restorations of those complex defects can only be provided
by bone graft substitutes. To fulfill the biological and mechanical functions of bone, ideal bone
substitutes require an interconnected pore network with adjustable pore sizes to promote bone
ingrowth combined with a simultaneous sufficient mechanical strength to withstand mechanical
loads [6–8]. The most promising materials are calcium phosphate-based ceramics (such as bioactive
hydroxyapatite or bioresorbable β-tricalciumphosphate) due to their chemical similarity to apatite,
the natural bone mineral, and the ability to form a strong bonding to natural bone [1]. To meet
these biological and mechanical criteria, various fabrication techniques for porous hydroxyapatite
(HAp) scaffolds were implemented including replica method [9–12], sacrificial templating [11,13–15],
direct foaming [10,14,16], freeze casting [7,17], extrusion [18] and additive manufacturing [19–22].
However, not only the low mechanical strength and toughness of monolithic porous HAp limits

Materials 2020, 13, 1907; doi:10.3390/ma13081907 www.mdpi.com/journal/materials

Materials 2020, 13, 1907 2 of 16

the application as load-bearing implants [1], also the fabrication of complex-shaped implants with a
controlled porosity on an industrial level remains so far unsolved. For that reason, bulk ceramic implants
are still manufactured by subtractive computer-aided milling (CAD/CAM process) of biocompatible
zirconia or alumina [23,24], while bioactive HAp is only used in coatings or for non-load-bearing bulk
implants [25]. Thus, there is a high demand to establish manufacturing techniques for HAp bone and
dental implants, which provide a near-net shaping of implants with complex geometries combined
with an adjustable porosity to enable an industrial fabrication of ideal patient-specific implants.
Ceramic injection molding (CIM) is a cost-effective industrial processing technique for
complex-shaped ceramic components with high dimensional accuracies [26–28]. Although CIM
enables the fabrication of near-net shaped ceramic implants, the technique itself does not provide
a simple and fast adjustability of the total porosity and pore sizes. So far, the porosity in porous
CIM was either introduced by variation of the solid loading in the ceramic-wax-feedstock [27],
partial sintering [26,29–32], direct foaming [33] or by using mixtures of coarse and fine raw powders [28].
Only for metal injection molding sacrificial templates have been used in the feedstock to generate
well-defined porosities after the thermal heat treatment [34–36]. Sacrificial templating is the most
straightforward manufacturing technique to tailor defined pore structures in a broad porosity range by
changing the amounts (20–90 Vol%), shapes (such as spheres or fibers) and sizes (1-700 µm) of the used
pore formers [37].
In this work, we present the fabrication of porous HAp implants with adjustable porosities and pore
sizes by combining injection molding with sacrificial templating. Feedstocks for porous ceramics were
fabricated by adding varied amounts (0–40 Vol%) of phenolic resin spheres as spherical pore formers to
the HAp-wax-feedstocks. The resulting microstructural and mechanical properties were investigated
in dependence of the pore former content. In addition, the properties of interpenetrating (3-3)
ceramic-polymer composites, manufactured by infiltrating a urethane dimethacrylate (UDMA)-based
monomer solution into the porous injection molded HAp preforms, will be discussed with regard to
their application as potential dental implants.

2. Material and Methods

2.1. Injection Molding of Porous Hydroxyapatite Ceramics

Porous hydroxyapatite (HAp) ceramics were fabricated utilizing ceramic injection molding
combined with the addition of sacrificial templates. Before use, the HAp raw powder (04238,
Sigma-Aldrich Corp., St. Louis, MO, USA) was calcined at 1000 ◦ C for 2 h and afterwards wet-milled
in a planetary mill (Pulverisette 6, FRITSCH GmbH, Idar-Oberstein, Germany) with 500 rpm for 10 min
in isopropanol using ZrO2 grinding balls (Ø = 2 mm, Tosoh Corp., Tokyo, Japan). After drying and
sieving (35 mesh), a deagglomerated powder with a mean particle size of d50 = 1.8 µm and a specific
surface area of Sv = 8.3 m2 /g was obtained. The milled powder was hydrophobized in dry hexane
(Merck KGaA, Darmstadt, Germany) using 0.65 mg/m2 stearic acid (Honeywell Specialty Chemicals
Seelze GmbH, Seelze, Germany) as surfactant. For the feedstock preparation the hydrophobized HAp
powder was dispersed in molten paraffin (Granopent P, Carl Roth GmbH, Karlsruhe, Germany) and
carnauba wax (naturfarben, Carl Roth GmbH, Karlsruhe, Germany) at 120 ◦ C for 12 h under continuous
stirring (RW 20 mixer, IKA-Werke GmbH & Co. KG, Staufen, Germany). The final HAp feedstock
contained 50.0 Vol% hydrophobized HAp powder, 44.9 Vol% paraffin wax and 5.1 Vol% carnauba wax.
Two kinds of phenolic resin spheres, type A (BRHF-035 Brace GmbH, Karlstein, Germany) and type B
(BRHF-250 Brace GmbH, Karlstein, Germany) differing by one order of magnitude, were used as pore
formers in this work. Figure 1 shows the microstructure of the two types of utilized pore formers and
the corresponding particle size distributions. The particle size distributions were determined by image
analysis of several SEM-micrographs for both types, analyzing more than 2000 spheres for the small
type A and more than 250 spheres for large type B, respectively. Mean particle sizes of dA 50
= 19.6 µm
and dB50 = 202.1 µm were measured for type A and type B spherical pore formers, respectively. For an
Materials 2020, 13, 1907 3 of 16

Materials 2020, 13, x FOR PEER REVIEW 3 of 17

easier understanding and a uniform nomenclature, the two types of resin spheres will in the entire
the two types of resin spheres will in the entire manuscript be classified by their size and called 20
manuscript be classified by their size and called 20 µm (= type A) and 200 µm (= type B) pore formers.
µm (= type A) and 200 µm (= type B) pore formers.

Figure
Figure 1. Microstructure(A,B)
1. Microstructure (A,B)and
andparticle
particle size
sizedistributions
distributions(C) of of
(C) thethe
type A (dA50 (d
type = 20 = 20and
50 µm) µm)type
and type
B (d50 = 200 µm) phenolic resin spheres utilized as spherical pore formers.
B (d 50 = 200 µm) phenolic resin spheres utilized as spherical pore formers.

Feedstocks
Feedstocks forforporous
porousceramics
ceramics were
werefabricated
fabricatedby by
adding various
adding amounts
various (0, 10, 20,
amounts (0,3010,and
20,4030 and
Vol%) of 20 µm pore formers to the 50 Vol% HAp feedstock. Additionally,
40 Vol%) of 20 µm pore formers to the 50 Vol% HAp feedstock. Additionally, a bimodal a bimodal pore size pore
distribution containing 15 Vol% of 20 µm and 5 Vol% of 200 µm spherical pore formers was realized.
size distribution containing 15 Vol% of 20 µm and 5 Vol% of 200 µm spherical pore formers was
The pore former containing HAp-feedstocks were homogenized for an additional mixing time of 12
realized. The pore former containing HAp-feedstocks were homogenized for an additional mixing
h before molding. The casting molds were manufactured utilizing a negative replica technique
time[29,38].
of 12 Positive
h beforepolymer
molding. The casting
preforms molds were
were 3D-printed with amanufactured
z-resolution of utilizing
30 µm with a negative
a SLA 3D-replica
technique
printer (Digitalwax® 028J, DWS S.r.l., Thiene, VI, Italy) and afterwards molded with a30PDMS
[29,38]. Positive polymer preforms were 3D-printed with a z-resolution of µm with a
SLAelastomer
3D-printer (Digitalwax ® 028J,Wacker
DWS S.r.l., Thiene, VI, Italy) Germany).
and afterwards
(Elastosil M 4643 A/B, Chemie AG, München, Plates molded with a PDMS
with dimensions
elastomer
of 35 mm(Elastosil
× 35 mm M× 4643
4 mmA/B,
and Wacker
complexChemie AG, München,
shaped facial, cranial andGermany). Plates
dental implants with
were dimensions of
3D-printed
and×molded.
35 mm 35 mm The× 4 mmfeedstocks were transfer
and complex shaped molded
facial,into the and
cranial negative PDMS
dental formswere
implants at 120 °C. The and
3D-printed
binder was thermally removed by wick debinding in an Al 2O3 nano-powder bed (AKP-50,
molded. The feedstocks were transfer molded into the negative PDMS forms at 120 C. The binder was ◦ Sumitomo
Chemical Co. Ltd., Tokyo, Japan) with a d50 of 200 nm. Afterwards the samples were sintered at 1250
thermally removed by wick debinding in an Al2 O3 nano-powder bed (AKP-50, Sumitomo Chemical
°C for 2 h with heating rates of 5 K·min−1. ◦
Co. Ltd., Tokyo, Japan) with a d50 of 200 nm. Afterwards the samples were sintered at 1250 C for 2 h
with2.2.
heating 5 K·min−1 .Composites
ratesofofHAp/UDMA
Fabrication
HAp/UDMA
2.2. Fabrication compositesComposites
of HAp/UDMA were fabricated by infiltration of porous HAp preforms (3–3 HAp/air
composites) with a liquid monomer mixture. As porous preforms, only HAp samples with 30 and 40
HAp/UDMA
Vol% pore formers composites
were used.were fabricated
For the monomerby infiltration
mixture, of porous
diurethane HAp preforms
dimethacrylate (UDMA, (3–3 HAp/air
Sigma
composites)
Aldrich Corp., St. Louis, MO, USA) and tryethylene glycol dimethacrylate (TEGDMA, Sigma Aldrich30 and
with a liquid monomer mixture. As porous preforms, only HAp samples with
40 Vol%
Corp.,pore formers
St. Louis, MO,were
USA) used. For the
were mixed in a monomer
molar ratio mixture,
of 1:1. 0.15diurethane dimethacrylate
wt% of benzoyl (UDMA,
peroxide (Sigma
Aldrich
Sigma Corp.,
Aldrich St. Louis,
Corp., MO, USA)
St. Louis, was added
MO, USA) to the monomer
and tryethylene glycolsolution, acting as thermal
dimethacrylate radicalSigma
(TEGDMA,
initiator
Aldrich for St.
Corp., theLouis,
polymerization
MO, USA) reaction. The monomer
were mixed in a molarsolution
ratio of was
1:1.homogenized
0.15 wt% of for 1 h onperoxide
benzoyl a
magnetic stirrer. The monomer infiltration was performed inside a desiccator
(Sigma Aldrich Corp., St. Louis, MO, USA) was added to the monomer solution, acting as thermal equipped with a
pressure-equalizing dropping funnel, allowing a simultaneous degassing of the porous HAp samples
radical initiator for the polymerization reaction. The monomer solution was homogenized for 1 h
and the monomer solution. The porous HAp plates were placed inside PDMS forms. Before
on a magnetic stirrer. The monomer infiltration was performed inside a desiccator equipped with a
infiltration the monomer solution and the porous HAp samples were degassed for 3 h with pressures
pressure-equalizing dropping
<2500 Pa. The infiltration funnel,
was allowing
performed a simultaneous
by dropwise additiondegassing of the porous HAp
of the UDMA/TEGDMA samples
solution
and through
the monomer solution. The porous HAp plates were placed inside PDMS forms.
the valve until the samples were fully covered, maintaining the vacuum for an additional 3Before infiltration
the monomer
h. After thesolution andthe
infiltration, thesamples
porous were
HApstored
samplesfor were
1 h atdegassed
atmospheric for pressure
3 h withandpressures <2500 Pa.
afterwards
The polymerized
infiltration wasat 130performed
°C for 3 h. by dropwise addition of the UDMA/TEGDMA solution through the
valve until the samples were fully covered, maintaining the vacuum for an additional 3 h. After the
2.3. Characterization
infiltration, the samples were stored for 1 h at atmospheric pressure and afterwards polymerized at
◦
130 C for For3 the
h. mechanical testing of the porous HAp and HAp/UDMA composites, bending bars with
dimensions 25 mm × 2.5 mm × 2 mm were manufactured by grinding off the excessive material with
2.3. aCharacterization
high precision surface grinding machine (MPS 2 R300, G&N Genauigkeits Maschinenbau Nürnberg
GmbH, Erlangen, Germany) and cutting with diamond wire saw (DWS175, Diamond WireTec GmbH
For the mechanical testing of the porous HAp and HAp/UDMA composites, bending bars with
dimensions 25 mm × 2.5 mm × 2 mm were manufactured by grinding off the excessive material with a
high precision surface grinding machine (MPS 2 R300, G&N Genauigkeits Maschinenbau Nürnberg
Materials 2020, 13, 1907 4 of 16

GmbH, Erlangen, Germany) and cutting with diamond wire saw (DWS175, Diamond WireTec GmbH &
Co. KG, Weinheim, Germany). To determine the open porosity, the bulk and true density of all samples
were determined by Archimedes’ principle according to DIN EN 623-2 in distilled H2 O [39]. The total
porosity was calculated from the geometric density by determining the dimensions and mass of the
bending bars. The closed porosity was calculated from the difference between total and open porosity.
The microstructure of fracture surfaces and polished cross-sections of both non-infiltrated and infiltrated
samples was investigated by scanning electronic microscopy (SEM Quanta 200, FEI Deutschland
GmbH, Frankfurt am Main, Germany). To visualize the interconnectivity of the pores and the resulting
polymeric UDMA network the HAp matrix of the HAp/UDMA composites was completely etched in
32 wt% hydrochloric acid solution (Merck KGaA, Darmstadt, Germany) for 2 days. The microstructure
of the etched polymer network was identically investigated. The surface-to-surface inter pore distance
was determined from SEM micrographs of polished surfaces by image analysis using a plugin for
nearest neighbor distance (NND) calculation of (FiJi) ImageJ. The 3D microstructure was additionally
characterized by micro computer tomography (µCT, Skyscan 1172, Bruker Micro CT, Kontich, Belgium)
with a resolution of 2.98 µm/voxel. The tungsten X-ray tube was operated with 80 kV and 100 mA
with a wavelength of λ = 0.024 nm, an 11 MP detector and an Al filter were used. The samples were
rotated for 180◦ with a rotation step size of 0.2◦ . The recorded 2D sinograms were reconstructed with
NRecon (Version 1.6, Bruker Micro CT, Kontich, Belgium) and 3D visualized using the software Amira
(Version 5.6, Thermo Fisher Scientific Inc., Waltham, MA, USA).
The Young’s moduli of the 25 mm × 2.5 mm × 2 mm bars were non-destructively measured by
impulse excitation method according to DIN EN 843-2 and ASTM-E1876 using a condenser microphone
(Audix TM-1, Audix Microphones, Wilsonville, OR, USA) and the software Buzz-o-sonic (Version 5.9,
BuzzMac International LLC, Glendale, WI, USA) [40,41]. The flexural strengths were determined in
4-point-bending tests (Instron 5565, Instron GmbH, Pfungstadt, Germany) according to DIN EN 843-1
with a support span of 20 mm and a constant crosshead speed of 0.5 mm·min−1 [42].

3. Results and Discussion

3.1. Microstructural and Mechanical Properties of the Porous Injection Molded HAp
After debinding and sintering (1250 ◦ C, 2 h) of the HAp samples containing 0 to 40 Vol% of
20 µm spherical pore formers, total porosities between 11.2 and 45.2 Vol% were obtained. The residual
sintering porosity of 11.2 ± 1.0 Vol% in the ceramic matrix without pore formers was considered
the optimum between almost complete densification and phase purity. At higher temperatures
(T ≥ 1300 ◦ C) the thermal decomposition of HAp (Ca10 (PO4 )6 (OH)2 ) to β-TCP (Ca3 (PO4 )2 ) and
TTCP (Ca4 (PO4 )2 O) was confirmed by XRD measurements (not shown here) in accordance with the
literature [43], thus preventing the fabrication of dense and phase-pure HAp ceramics from a feedstock
with 50 Vol% solid loading. Figure 2A shows the total porosity and the corresponding fractions of the
open and closed porosity in dependence of the pore former content. A mean pore size of d50 = 22.5 µm
and an average linear shrinkage of 18.3% ± 0.6% were determined, which both were found to be
independent of the examined pore former content. The measured mean pore size agrees well with the
initial pore former size of the 20 µm spheres.
The direct proportionality between the total porosity and the pore former content, shown by the
linear regression (R2 = 0.995) of Figure 2A, shows the free adjustability of the porosity by utilizing
varied amounts of sacrificial templates as pore forming agents [37]. The corresponding microstructure
of the 20 µm phenolic resin spheres containing samples are shown for a pore former content of 10, 20
and 40 Vol% in the SEM micrographs of Figure 3.
Materials 2020, 13, x FOR PEER REVIEW 5 of 17

Materials 2020, 13, 1907 5 of 16

Materials 2020, 13, x FOR PEER REVIEW 5 of 17

Figure 2. Porosity fractions (total, open and closed) of the porous hydroxyapatite (Hap) samples in
dependence of the pore former content containing 20 µm spherical pore formers (A): The linear fit of
(A) shows the linear relation (continuous line) between the total porosity and the pore former content,
the dashed lines are only a guidance for the eye. (B) shows the dependence of the real surface-to-
surface inter pore distance (data points represented by square symbols), determined by image
Figure
analysis2.
Figure Porosity
2.from
Porosity fractions (total,
fractions
SEM-micrographs, (total,on
open
open and
poreclosed)
theand formerof
closed) the
the porous
ofcontentporous hydroxyapatite
hydroxyapatite
for the 20 µm spherical (Hap)
(Hap) samples
samples
pore formers. in
in
dependence
dependence of the pore
of the data former
pore was
former content containing
content tocontaining 20 µm
20of
µm spherical
sphericalpore formers (A): The linear fit of (A)
The experimental compared the model Equation (1)pore formers
inserting the(A): The linear
measured fit of
particle
shows
(A) the linear relation (continuous line) between the total porosity andand
the the
porepore
former content, the
sizeshows the linear
distribution relation
of the 20 µm(continuous
spheres ofline) between
Figure thematerial
1 C (see total porosity
and methods, hereformer content,
highlighted in
dashed
the blue lines
dashed are only
lines and a guidance
are only for
a guidance the eye. (B) shows the dependence of the real surface-to-surface
section) for different porefor theincluding
sizes eye. (B) shows the 200
5, 100 and dependence
µm (dashed of the real surface-to-
lines).
inter pore distance (data points represented by square symbols), determined by image analysis from
surface inter pore distance (data points represented by square symbols), determined by image
SEM-micrographs,
The direct on the porebetween
proportionality former content for porosity
the 20 µmand spherical poreformer
formers.content,
The experimental
analysis from SEM-micrographs, on thethe total
pore former content the
for pore
the 20 µm spherical poreshown
formers. by the
data was compared to the model of Equation (1) inserting the measured particle size distribution of the
linearThe
regression
experimental (R² =data
0.995)
was of Figure 2A,
compared to theshows
modelthe free adjustability
of Equation (1) insertingof the
the measured
porosity by utilizing
particle
20 µm spheres of Figure 1C (see material and methods, here highlighted in the blue section) and for
varied
sizeamounts
distributionofof sacrificial templates
the 20 µm spheres as 1pore
of Figure C (seeforming
material and agents [37].here
methods, The corresponding
highlighted in
different pore sizes including 5, 100 and 200 µm (dashed lines).
the blue section)
microstructure of the and
20forµmdifferent
phenolic pore sizesspheres
resin including 5, 100 andsamples
containing 200 µm (dashed
are shown lines).
for a pore former

The direct proportionality between the total porosity and the pore former content, shown by the
linear regression (R² = 0.995) of Figure 2A, shows the free adjustability of the porosity by utilizing
varied amounts of sacrificial templates as pore forming agents [37]. The corresponding
microstructure of the 20 µm phenolic resin spheres containing samples are shown for a pore former
content of 10, 20 and 40 Vol% in the SEM micrographs of Figure 3.

Figure 3.3. SEM-micrographs

SEM-micrographsofof fracture
fracture surfaces
surfaces showing
showing the microstructure
the microstructure of the HAp
of the porous porous HAp
samples
samples containing
containing 10 (A,D),1020(A,D),
(B,E) 20
and(B,E) and 40
40 (C,F) (C,F)ofVol%
Vol% 20 µm of spherical
20 µm spherical pore formers.
pore formers. The lower
The lower 250×
250× magnification
magnification imagesimages
of (A–C) ofdisplay
(A–C) the
display the homogeneous
homogeneous distribution
distribution of the pores,ofwhile
the pores, while
the higher the
1000×
higher 1000× magnification images of (D–F) show the change of connectivity from
magnification images of (D–F) show the change of connectivity from isolated to interconnected pores. isolated to
interconnected pores.
Homogeneous pore distributions
Figure 3. SEM-micrographs of fracture were achieved
surfaces showing independent fromof the
the microstructure examined
the porous HAp pore
formersamples containing 10 (A,D), 20 (B,E) and 40 (C,F) Vol% of 20 µm spherical pore formers. The lower due
content, showing a good homogenization of the pore formers in the HAp-wax-suspensions
to the250×
wetmagnification
mixing process,images Figure
of (A–C)3. Up to a volume
display content ofdistribution
the homogeneous 20 Vol% pore formers,
of the the majority
pores, while the
higher 1000× magnification images of (D–F) show the change of connectivity from isolated to
interconnected pores.
Materials 2020, 13, 1907 6 of 16

of the pores are isolated and thus closed, which was optically confirmed by the SEM micrographs
of Figure 3B,E. At higher pore former contents (30 and 40 Vol%) cell windows between adjacent
pores are formed and interconnected, open-porous networks with closed porosities less than 2.4 Vol%
are generated, Figure 3C,F. Interconnected pore networks are mandatory to ensure the biological
integration of implants associated with a complete vascularization and rapid bone ingrowth [44].
The transition from isolated closed pores to an interconnected, open pore network can be described by
percolation models and the percolation threshold, representing the critical pore volume content [45–48].
The determination of the percolation threshold (Φc ) for interconnected pore networks is however
extremely complex as it strongly depends on several pore parameters such as the shape [46,47], size [48],
distribution [45] and packing density [49] and will therefore mainly be determined by the choice and
dispersion of the utilized pore formers. For spherical pore networks a theoretical percolation threshold
of Φc = 28.965 Vol% [47] is expected, agreeing well with the complete open porosity found in this work
at a pore former content of 30 Vol% for 20 µm spherical pore formers. Additionally, the observed closed
porosity at 20 Vol% and complete open porosity at 30 Vol% of the 20 µm pore formers is consistent with
porous gelcasted Ti, where comparable pore former sizes were used [50]. For a reasonable estimation
of the percolation threshold for differently sized pore formers, we propose to determine the mean
surface-to-surface inter pore distance hTi. The surface-to-surface interpore distance hTi of spherical
pores (transferred from the interparticle distance of spherical inclusions in particle composites) is given
by [51]:
1
π D

hTi = ξ dp − dp (1)
2αΦ
where dp is the mean pore size, Φ the pore former content, ξ and α are distributional constants
and D describes the dimension of the system with D{1, 2, 3}. The real surface-to-surface interpore
distance was determined by image analysis of the polished SEM-micrographs calculating the nearest
neighbor distance (NND) between the individual pores. Figure 2B shows the experimental interpore
distance hTi in dependence of the pore former content (Φ) in comparison to model of Equation (1)
inserting ξ ≈ 1, α = 3 and D = 3 and different pore former sizes (dp ). With increasing pore former
content the experimentally determined interpore distance hTi decreases and reaches 0.4 µm for 40 Vol%
pore formers approaching 0 within the standard deviations, Figure 2B. An acceptable agreement
of the experimental determined hTi with the fitted model of Equation (1) was found, inserting the
particle distribution of the 20 µm spheres (highlighted as the blue section of Figure 2B). A mean
surface-to-surface interpore distance of hTi ≤ 0 describes vividly the formation of an interconnected
pore network between adjacent pores. Mathematically, the zero point of Equation (1) (hTi = 0) equals
Φc = π/6 =ˆ 52.36 Vol% independent from the pore former size dp (inserting ξ ≈ 1, α = 3 and D = 3).
For practical use, however, the approximation to the zero point of the simple Equation (1) for different
dp allows a reasonable theoretical estimation of the percolation threshold Φc . As shown in Figure 2B,
pore sizes of <20 µm show an asymptotic convergence to hTi = 0 approaching the zero point of
Equation (1), while larger pore sizes such as 100 or the 200 µm spheres (type B) require a volume
content of Φc = 52.36 Vol% to obtain an interconnected pore network. In Table 1, all mentioned physical
properties of the porous HAp ceramics are summarized.

Table 1. Physical properties of the porous HAp ceramics containing 0–40 Vol% of 20 µm spherical
pore formers.

Pore Former Open Porosity (Φp ) Total Interpore Young’s Modulus Flexural Strength
Content/Vol% /Vol% Closed/Vol% /Vol% Distance hTi/µm (E)/GPa (σf )/MPa
0 0.6 ± 0.4 10.6 ± 1.2 11.2 ± 1.0 - 97.3 ± 1.9 69.0 ± 10.9
10 1.4 ± 0.4 14.9 ± 1.3 16.3 ± 1.3 11 83.1 ± 3.9 51.1 ± 12.5
20 3.4 ± 0.7 25.4 ± 1.5 28.8 ± 1.7 4.9 57.0 ± 2.5 31.4 ± 5.6
30 34.7 ± 0.9 2.1 ± 1.5 36.8 ± 1.4 1.8 42.8 ± 3.1 18.1 ± 2.3
40 42.8 ± 1.6 2.4 ± 1.4 45.2 ± 0.9 0.4 29.1 ± 0.9 13.0 ± 3.0
 Closed
Content /Vol% /Vol% 〈𝑻〉 (E) (σf)
/Vol% /Vol%
/µm /GPa /MPa
0 0.6 ± 0.4 10.6 ± 1.2 11.2 ± 1.0 - 97.3 ± 1.9 69.0 ± 10.9
10 1.4 ± 0.4 14.9 ± 1.3 16.3 ± 1.3 11 83.1 ± 3.9 51.1 ± 12.5
Materials 2020, 13, 1907 7 of 16
20 3.4 ± 0.7 25.4 ± 1.5 28.8 ± 1.7 4.9 57.0 ± 2.5 31.4 ± 5.6
30 34.7 ± 0.9 2.1 ± 1.5 36.8 ± 1.4 1.8 42.8 ± 3.1 18.1 ± 2.3
40
The mechanical 42.8 ± 1.6
properties 2.4
of ±the
1.4porous45.2 ± 0.9ceramics
HAp 0.4 were investigated
29.1 ± 0.9 in13.0 ± 3.0
terms of Young’s
modulusTheand flexural strength by impulse excitation method and four-point bending.
mechanical properties of the porous HAp ceramics were investigated in terms of Young’s
Figure 4A
shows the mechanical
modulus properties
and flexural strength as
byaimpulse
functionexcitation
of the total porosity
method and and pore former
four-point content.
bending. Figure A4Ageneral
decrease in Young’s modulus and flexural strength was observed with increasing porosity. The
shows the mechanical properties as a function of the total porosity and pore former content. A general Young’s
modulus and
decrease inflexural
Young’s strength
modulus could be tailored
and flexural in awas
strength broad range with
observed fromincreasing
97.3 to 29.1 GPa and
porosity. The69.0 to
13.0Young’s modulus andby
MPa, respectively, flexural
addingstrength couldof
0–40 Vol% bepore
tailored in a broad range from 97.3 to 29.1 GPa and
formers.
69.0 to 13.0 MPa, respectively, by adding 0–40 Vol% of pore formers.

Figure 4. Mechanical
Figure 4. Mechanical properties of the
properties of porous HApHAp
the porous ceramics and and
ceramics HAp/urethane dimethacrylate
HAp/urethane (UDMA)
dimethacrylate
composites: Young’s modulus
(UDMA) composites: Young’sand flexural
modulus andstrength
flexuralofstrength
the porous HAp
of the ceramics
porous HAp in dependence
ceramics in of
dependence of the total porosity (A) and Young’s modulus and Vickers hardness of
the total porosity (A) and Young’s modulus and Vickers hardness of the HAp/UDMA composites inthe HAp/UDMA
composites
dependence ofinthe
dependence of the UDMA-polymer
UDMA-polymer content (B). content (B).

TheThe porosity
porosity dependenceof
dependence of the
the Young’s
Young’s modulus
modulusand flexural
and flexuralstrength can be
strength candescribed by theby the
be described
well-established, semi-empirical power-law approach of Phani
well-established, semi-empirical power-law approach of Phani [52]:[52]:
𝑀 =𝑀 (1 − 𝛼𝛷 )  (2)
n
where the mechanical property (E, σf) ofM p =
the porous 1 − αΦM
M0 ×material p p is given by the modulus of the dense (2)
material M0, the porosity (Φp), the packing geometry factor α = 1–3.85 and the pore shape and
where the mechanical
orientation property
related exponent n = (E,
2–7 σ f ) of the
[52,53]. porous
A good material
agreement wasMobtained
p is given by thethemodulus
by fitting model of of the
dense material M
Equation (2) to the0 , the porosity (Φ ), the packing geometry factor α = 1–3.85 and
experimental data for both Young’s modulus (R² = 0.9998) and flexural strength
p the pore shape
and(R²orientation related exponent n = 2–7 [52,53]. A good agreement was obtained
= 0.9818) assuming α = 1. The mechanical properties of dense and porous HAp depend strongly by fitting the
model of Equation
on the (2) to the
powder synthesis experimental
and data for
purity, the utilized both Young’s
fabrication modulus
technique and thus 2 = 0.9998)
(R the resultingand
grain flexural
strength = 0.9818)
(R2 residual
size and porosity,
assuming α = 1.
leading to The
greatmechanical
variations ofproperties
reported literature
of dense values [1,54–56].
and porous HAp Thedepend
∗
determined E0 = 131 GPa is consistent with values for dense HAp 𝐸 = 80–140 GPa reported in the
strongly on the powder synthesis and purity, the utilized fabrication technique and thus the resulting
literature
grain size and [54–56]
residualand the corresponding
porosity, leadingnto= great
2.49 is variations
close to theofvalues for ideal
reported isotropic
literature materials
values [1,54–56].
with spherical pores n = 2–2.3 [57,58]. A stronger decrease was observed for∗ the flexural strength with
The determined E0 = 131 GPa is consistent with values for dense HAp E0 = 80–140 GPa reported in the
literature [54–56] and the corresponding n = 2.49 is close to the values for ideal isotropic materials
with spherical pores n = 2–2.3 [57,58]. A stronger decrease was observed for the flexural strength
with n = 3.69 and σ0 = 104 MPa, which agrees well with the typical values for commercial dense
HAp σ∗0 ≈ 100–120 MPa [1,56], although also much lower and higher values of 35 to 350 MPa have
been reported [54]. The introduction of porosity allows a tailoring of the biological properties such
as vascularization, bone ingrowth and resorption rates as well as the mechanical properties, like a
reduction of the high stiffness compared to human bone to avoid stress shielding [59], however it is
inevitably associated with a loss of mechanical strength. The fabrication of HAp-polymer composites
is an attractive design approach to overcome these negative influencing factors and to further tailor the
properties of future implants to the human body.

3.2. Microstructural and Mechanical Properties of the Interpenetrating HAp/UDMA Composites

The interconnected pore networks, formed by 30, 40 Vol% or higher amounts of pore formers
incorporated in HAp ceramics, may serve as porous ceramic preforms for the fabrication of polymer
Materials 2020, 13, 1907 8 of 16

infiltrated ceramic networks (PICNs), which belong to the class of interpenetrating (3–3) composites.
Based on the advantages associated with the homogeneous, interconnected 3D distribution of
both phases, PICNs have recently gained great interest to replace the widely used all-ceramic and
resin-based ceramic particle-polymer (0–3) composites for dental restorations [60–63]. The properties of
PICNs are more adapted to the hardness and stiffness of natural enamel and dentin than ceramics and in
comparison to particle composites they exhibit a superior mechanical strength, stiffness, toughness and
improved wear resistance [60–63]. In this work interpenetrating HAp/UDMA composites (IPCs) were
manufactured by infiltrating a UDMA-TEGDMA monomer solution into the porous HAp preforms
with 30 and 40 Vol% pore formers and a subsequent polymerization step. In Table 2, the microstructural
and mechanical properties of the HAp/UDMA composites are summarized in reference to both
pure materials.

Table 2. Microstructural and mechanical properties of the interpenetrating HAp/UDMA composites

and pure reference materials.

Geometric Theoretical Flexural

Preform Porosity Vickers Hardness Young’s Modulus
Samples Density Density Strength
/Vol% /g·cm−3 /% HV1/GPa /GPa /MPa
Pure HAp - 2.81 ± 0.05 88.8 4.5* 131** 104**
30 Vol% Inf. 36.8 ± 1.4 2.29 ± 0.05 97.6 2.12 ± 0.31 46.1 ± 2.1 29.6 ± 5.5
40 Vol% Inf. 45.2 ± 0.9 2.10 ± 0.04 94.9 1.15 ± 0.18 31.8 ± 3.3 19.7 ± 3.9
Pure
- 1.20 ± 0.01 - 0.2 ± 0.04 3.9 ± 0.3 97.3 ± 21.4
UDMA/TEGDMA
* Data taken from literature [8], ** E0 and σ0 were extrapolated for dense HAp from Equation (2).

The SEM-micrographs of Figure 5A,B show the corresponding microstructure of the HAp/UDMA
composites. Almost dense HAp/UDMA composites with theoretical densities of 97.6% and 94.9% were
obtained for the porous HAp preforms containing 30 Vol% and 40 Vol% of pore formers, confirmed
by the polymer-filled pores of Figure 5A. A complete infiltration (TD > 99%) could not be achieved
based on the polymerization shrinkage of the monomer solution mixture, highlighted by the orange
arrows of Figure 5A,B. For the pure UDMA/TEGDMA (1:1 mol) mixture a linear polymerization
shrinkage of 9.0% ± 0.1% was measured, which is within the values reported of the pure constituents
(UDMA: 8.7% ± 0.03% and TEGDMA: 14.1% ± 0.32%) [64]. Assuming a complete infiltration (100%)
of the total pore volume for both preforms, the determined polymerization shrinkage of 9.0% causes
porosities of 3.3% and 4.1% for an isotropic shrinkage, agreeing well with the measured theoretical
densities (Table 2). To achieve fully densified PICN composites a pressure-assisted polymerization with
pressures up to 300 MPa have to be applied additionally to the usage of coupling agents to improve
the adhesion between polymer and ceramic [63,65,66]. However, in contrast to the small pore sizes
(~1 µm) of typical PICN ceramic preforms fabricated by partial sintering, the utilized pore formers
(~20 µm) of this work enable a significant decrease of the required infiltration pressure. The infiltration
pressure for a cylindric pore with a radius r can be estimated by using the Hagen–Poiseuille law,
where the applied pressure difference ∆p is proportional to 1/r4 [67]. Under identical test conditions,
the infiltration pressure of ∆p1 = 300 MPa can be reduced to ∆p2 = 2 × 10−3 MPa by increasing the
pore size from d1 = 1 µm to d2 = 20 µm (using ∆p2 = (r1 /r2 )4 × ∆p1 ), showing that for the simplified
model no external pressure is required to infiltrate the porous HAp preforms. Regardless of that fact,
an interconnected, cohesive polymeric network consisting of interconnected UDMA-based spheres was
successfully realized by pressureless infiltration, as shown in the etched SEM-micrograph of Figure 5C
and the µCT-derived reconstructed, skeletonized polymer network of Figure 5D. The color heat-map
of the skeletonized polymer network represents the pore sizes with blue for pores >1 µm and red for
pores >10 µm. A highly interconnected polymer network was obtained, in which the spherical pore
formers (>10 µm) were connected via small cell windows, for which the size was between 1 and 10 µm.
Materials 2020, 13, 1907 9 of 16
Materials 2020, 13, x FOR PEER REVIEW 10 of 17

Figure 5. Microstructure
Microstructureofofthe thefabricated
fabricated HAp/UDMA
HAp/UDMA composites
composites withwith 40 Vol%
40 Vol% of formers
of pore pore formers
(A,B):
(A,B): SEM-micrographs show the complete polymer infiltration of all HAp
SEM-micrographs show the complete polymer infiltration of all HAp pores (A) and polymerization pores (A) and
polymerization
shrinkage at theshrinkage
HAp/UDMA at the HAp/UDMA
interface, interface,
highlighted by thehighlighted
orange arrows by the
(B). orange arrowsof (B).
Visualization the
Visualization
interconnectedofUDMA-based
the interconnected
polymer UDMA-based
network (C,D):polymer network (C,D):
SEM-micrograph afterSEM-micrograph
etching-out the HApafter
etching-out the (C)
ceramic matrix HAp andceramic matrix skeletonized
reconstructed, (C) and reconstructed,
µCT-polymer skeletonized µCT-polymer
network indicating network
the pore sizes
indicating the pore sizes
by a color heat-map withby a color
blue for pores >1 µm
heat-map with
andblue
red for
color >10>1
pores µmµm and
(D). red color
Fracture >10 µmof(D).
behavior the
Fracture
HAp/UDMA behavior of the HAp/UDMA
composites (E,F): The twocomposites
fracture(E,F): The of
surfaces twoonefracture
samplesurfaces
from theof one sample
flexural from
testing,
the flexural
showing thetesting,
fractureshowing the fracture at the
at the polymer/ceramic polymer/ceramic
interface associated withinterface
100%associated with 100%
pullout effects of all
pullout effects
polymeric of allhighlighted
spheres, polymeric spheres, highlighted
as exemplary by threeasred
exemplary by three red arrows (E,F).
arrows (E,F).

The mechanical
3.3. Potentials properties
and Future of the
Perspectives of composites were
the Porous HAp investigated
Ceramics in dependence
and HAp/UDMA of the infiltrated
Composites
polymer content, Figure 4B. The rule of mixtures (ROM) of Reuss and Voigt were used to theoretically
Ceramic injection molding (CIM) coupled with sacrificial templating facilitates the
describe the influence of the phase contents on the hardness and Young’s modulus, Equation (3) [68,69].
manufacturing of porous ceramics with complex geometries, tailored pore sizes and porosities, which
Additionally, the lower and upper Hashin–Shtrikman (HS) bounds were applied to more precisely
may serve as restorative bone implants for critical bone defects. The microstructural and mechanical
properties are directly determined by the amount, size and shape of the utilized pore former [37].
The mechanical properties of the porous HAp ceramics and interpenetrating HAp/UDMA
composites are shown in Table 3 in comparison to human bone, teeth and other UDMA-based PICNs.
Materials 2020, 13, 1907 10 of 16

model the experimental data of the Young’s modulus, Equation (4) [70,71]. For the pure reference
materials, the values shown in Table 2 were used to fit the ROM- and HS-bounds.
!−1
ΦA (1 − ΦA )
Mc = ΦA MA + (1 − ΦA )MB , MC = + (3)
MA MB

EA (ΦA EA + (2 − ΦA ) EB ) EB ((1 − ΦA )EB + (1 + ΦA ) EA )

EC,upper = , EC,lower = (4)
ΦA EB + (2 − ΦA ) EA (1 − ΦA )EA + (1 + ΦA ) EB
The mechanical properties Mc (or Ec , respectively) of the composite are given by the volume
fraction Φ and the mechanical property Mi (here Young’s modulus and Vickers hardness) of the
constituents A and B. A general decrease of both Young’s modulus and Vickers hardness with
increasing polymer content was observed. All experimental data points were within the calculated
ROM and HS-bounds, agreeing well with the models of Equations (3) and (4) for hardness and Young’s
modulus. However, the HAp/UDMA composites exhibited a lower flexural strength than the pure
components (Table 2), which can be attributed to the poor interface adhesion caused by the discussed
polymerization shrinkage. Nevertheless, the polymer infiltration lead to a significant increase in the
flexural strength of +64% (to 29.6 ± 5.5 MPa) and +52% (to 19.7 ± 3.9 MPa) in comparison to the porous
Hap that preforms with 30 and 40 Vol% of pore formers, respectively. Figure 5E,F shows the two
fracture surfaces of one HAp/UDMA composite with 40 Vol% pore formers highlighting the typical
fracture behavior of the composites. The fracture always occurred at the polymer-ceramic interface
leading to complete pullout of all polymeric spheres (100% pull-out), shown in the mirrored fracture
surfaces. Pullout effects in weak-interface composites are one of the most promising crack deflection
mechanisms dissipating high crack energies, which can enhance the fracture toughness and crack
resistance [72,73].

3.3. Potentials and Future Perspectives of the Porous HAp Ceramics and HAp/UDMA Composites
Ceramic injection molding (CIM) coupled with sacrificial templating facilitates the manufacturing
of porous ceramics with complex geometries, tailored pore sizes and porosities, which may serve as
restorative bone implants for critical bone defects. The microstructural and mechanical properties are
directly determined by the amount, size and shape of the utilized pore former [37]. The mechanical
properties of the porous HAp ceramics and interpenetrating HAp/UDMA composites are shown in
Table 3 in comparison to human bone, teeth and other UDMA-based PICNs. For the used 20 µm
spherical pore formers, the monolithic porous HAp ceramics exhibit mechanical properties between
trabecular and cortical bone.

Table 3. Mechanical properties of the monolithic porous HAp ceramics and interpenetrating
HAp/UDMA composites in comparison to human bone, teeth and UDMA-based polymer infiltrated
ceramic networks (PICNs).
Young’s Vickers Flexural
Porosity
Monolithic Ceramic Material Modulus Hardness Strength Reference
/Vol% /GPa /GPa /MPa
Cortical Bone 5–10 7–30 - 50–150 [8,43,74]
Bone restoration Trabecular bone 75–95 0.05–0.5 - 10–20 [43,74]
Porous HAp 11.2–45.2 29–97 - 13–69 This work
Polymer Young’s Vickers Flexural
PICN Material Content Modulus Hardness Strength Reference
/Vol% /GPa /GPa /MPa
Enamel - 48–105 3–5.3 76 [74,75]
Dentin - 11–20.3 0.5–1.0 245–268 [74,75]
Dental restoration HAp/UDMA*,a 37–45 32–46 1.2–2.1 20–30 This work
Feldspar/UDMA**,a 28–41 16–28 1.1–2.1 131–160 [65]
ZrO2 /UDMA**,a 8–42 15–101 0.4–10.8 58–212 [66]
* pressureless polymerization, ** high pressure, high temperature polymerization, a excluding the properties of the
pure constituents.
Materials 2020, 13, 1907 11 of 16

Based on the poor fracture toughness of monolithic HAp (~1.0 MPa·m0.5 ) [2,43], the porous HAp
ceramics of this work can only be applied for non-load bearing applications. The combination of CIM
and the 3D-printing process for the mold fabrication allows a flexible, near-net shape manufacturing
of complex shaped implants. The patient-specific defect information including exact shape, size and
surrounding bone density can be obtained from CT-scans, which afterwards can be implemented in
the 3D-printing CAD files to generate patient individualized implants. Figure 6C shows exemplary
fabricated cranial and maxillofacial HAp implants, which are inserted in a 3D-printed skull model.
For the implant fabrication, the sintering shrinkage has to be considered, which with 18.3% ± 0.6% was
found to be independent of the examined pore former content. The density, strength and stiffness of the
HAp implants (Figure 4A) can then easily be adjusted to the age- and gender-related defect-surrounding
bone density by changing the amounts of the utilized pore formers to avoid stress shielding effects.
Although interconnected pore networks consisting of 20 µm spherical pore formers were successfully
generated, for an efficient vascularization and bone ingrowth larger pore formers >250 µm have to be
used [2]. To highlight the microstructural flexibility of the utilized fabrication technique, porous HAp
ceramics with bimodal pore size distributions containing 5 Vol% of 200 µm and 15 Vol% of 20 µm
spheres were fabricated, Figure 6A. As shown in Figure 6A, crack-free samples with homogeneously
distributed bimodal pores, which differ by one order of magnitude, were successfully fabricated.
Moreover, the technique is not only limited to the fabrication of homogenously distributed samples,
but also enables designing of ceramics with a graded porosity. Figure 6B shows the defect-free interface
of a graded porous HAp sample with 20 Vol% (left) and 40 Vol% (right) spherical pore formers (20 µm).
Bioactive ceramics with graded porosity are the next generation biomaterials in tissue engineering to
overcome the poor mechanical properties of monolithic porous ceramics (such as HAp) and to improve
the biological integration by an enhanced nutrient transfer and osteogenic differentiation [76–78].
The properties of the porous injection molded HAp ceramics can further be tailored by combining
the stiff ceramic matrix with a comparable soft UDMA-based polymer to form an interpenetrating
composite, achieving properties, which cannot be obtained with the pure constituents, Table 2.
Although the poor flexural strength of the HAp/UDMA composites requires future improvements
in the manufacturing process (utilizing high pressure and temperature polymerization and coupling
agents [63,65,66]), the achieved stiffness and hardness are comparable to natural enamel, dentin and
other (commercial) PICNs and thus do not require further improvements for these types of
applications [64,66,74,75], Tables 2 and 3. The adaption of the stiffness and hardness to the properties
of natural teeth is essential to avoid stress shielding effects and excessive wear of the antagonist [65].
In comparison to other PICNs, an additional advantage of HAp/UDMA material systems arises from
the chemical similarity of HAp to the natural bone and teeth mineral providing strong bonding to
surrounding bone tissue (osteoconduction) and therefore an enhanced mechanical anchoring of the
implant. Restorative dental implants are commonly fabricated via subtractive CAD/CAM machining
providing high accuracies but also high material waste, which cannot easily be recycled [23,24,65].
The utilized porous injection molding has great potential to design near-net shaped dental implants,
which afterwards can be processed to PICNs by liquid polymer infiltration, to reduce processing steps
and waste.
Materials 2020, 13, 1907 12 of 16
Materials 2020, 13, x FOR PEER REVIEW 12 of 17

Figure 6.6. Future

Figure Future perspectives
perspectives forfor porous
porous HApHAp ceramics
ceramics and
and HAp/UDMA
HAp/UDMA composites
composites fabricated
fabricated by
by
porous
porousinjection
injection molding:
molding: Microstructure
Microstructure of a porous HAp sample
of a porous HAp with a bimodal
sample with apore size distribution
bimodal pore size
containing
distribution 5 Vol% of 200 µm
containing and of
5 Vol% 15 200
Vol% µmof 20
andµm15spherical
Vol% of pore
20 µm formers (A).pore
spherical Polished SEM-micrograph
formers (A). Polished
of a HAp sample with a graded porosity, showing the defect-free interface between
SEM-micrograph of a HAp sample with a graded porosity, showing the defect-free interface two layers containing
between
20 Vol% and 40 Vol% of 20 µm spherical pore formers (B). Potential non-load bearing
two layers containing 20 Vol% and 40 Vol% of 20 µm spherical pore formers (B). Potential non-load cranial (1) and
maxillofacial (2) implants for the porous HAp ceramics (C). Fabricated porous HAp bending
bearing cranial (1) and maxillofacial (2) implants for the porous HAp ceramics (C). Fabricated porous bars with
0,
HAp10 and 30 Vol%
bending barsofwith
pore0,formers
10 and 30(1) Vol%
and potential two-part
of pore formers (1)dental implantstwo-part
and potential for the interpenetrating
dental implants
HAp/UDMA
for the interpenetrating HAp/UDMA composites (2), showing a ceramic crown and with
composites (2), showing a ceramic crown and three types of abutments threedifferent
types of
anchoring geometries (D).
abutments with different anchoring geometries (D).
4. Conclusions
The properties of the porous injection molded HAp ceramics can further be tailored by
In
combiningthis work, we demonstrated
the stiff ceramic matrix the fabrication of porous hydroxyapatite
with a comparable soft UDMA-based ceramics with well-defined
polymer to form an
porosities and pore
interpenetrating sizes by combining
composite, achieving ceramic injection
properties, which molding
cannotwithbe the addition
obtained withof sacrificial
the pure
templates.
constituents, The novelty
Table of this fabrication
2. Although the poor technique is the near-net
flexural strength shape manufacturing
of the HAp/UDMA composites of complex
requires
shaped bone grafts with controlled porosity and connectivity. Their microstructural
future improvements in the manufacturing process (utilizing high pressure and temperature and mechanical
properties can beand
polymerization directly adjusted
coupling agentsto[63,65,66]),
the age- and thegender-related
achieved stiffness defect-surrounding
and hardness arebone density
comparable
of patients by changing the amount, size and shape of the utilized
to natural enamel, dentin and other (commercial) PICNs and thus do not require further pore formers to avoid stress
shielding effects. The inherent brittleness of the monolithic HAp limits the usage
improvements for these types of applications [64,66,74,75], Tables 2 and 3. The adaption of the to non-load bearing
applications
stiffness and(e.g., cranialtoorthe
hardness maxillofacial
properties implants).
of natural We teethdemonstrated
is essential totheavoid
feasibility
stressofshielding
manufacturing
effects
interpenetrating HAp/UDMA composites with tremendous potential for use as
and excessive wear of the antagonist [65]. In comparison to other PICNs, an additional advantage of restorative dental
implants.
HAp/UDMA Based on the chemical
material and physical
systems arises from the similarity
chemical of similarity
HAp to theofnatural
HAp to bone
theand toothbone
natural mineral,
and
rejection reactions
teeth mineral and excessive
providing wear oftothe
strong bonding antagonists
surrounding maytissue
bone be prevented. Although
(osteoconduction) anduptherefore
to now
the
an determined flexural strength
enhanced mechanical requires
anchoring further
of the optimizations,
implant. Restorative thedental
investigated
implantsYoung’s modulus
are commonly
and hardness
fabricated viawere comparable
subtractive to natural
CAD/CAM dentin, enamel
machining and high
providing otheraccuracies
already commercialized
but also high polymer
material
infiltrated network (PICN) materials and meet the requirements of the medical profession.
waste, which cannot easily be recycled [23,24,65]. The utilized porous injection molding has great However,
potential to design near-net shaped dental implants, which afterwards can be processed to PICNs by
liquid polymer infiltration, to reduce processing steps and waste.
Materials 2020, 13, 1907 13 of 16

in contrast to the commonly used subtractive CAD/CAM machining of PICNs, the here presented
near-net shape fabrication technique does not require further post processing and thus does not produce
waste as the complex dental implants can be directly obtained via the ceramic injection molding and
afterwards can be processed to PICNs.

Author Contributions: Conceptualization, J.B. and T.F.; Experimental work, P.H., S.S., I.H. and P.M.;
formal analysis, J.B.; writing—original draft preparation, J.B.; writing—review and editing, J.B. and T.F.; project
administration, T.F.; supervision, T.F.; funding acquisition, T.F. All authors have read and agreed to the published
version of the manuscript.
Funding: The financial support of the Emerging Fields Initiative of Friedrich-Alexander-University
Erlangen-Nuernberg (Project: MoJo 3D-Modular composite Joint 3D) is gratefully acknowledged.
Acknowledgments: The authors additionally thank the BRACE GmbH for providing the phenolic resin spheres
used as pore formers in this work.
Conflicts of Interest: The authors declare no conflict of interest.

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